Hydrolytic kinetic resolution of terminal mono- and bis-epoxides in the synthesis of insect pheromones: routes to (-)-(R)- and (+)-(S)-10-methyldodecyl acetate, (-)-(R)-10-methyl-2-tridecanone, (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol), (-)-(1R,7R)-1,7-dime

Hydrolytic kinetic resolution (HKR) of functionalised epoxides using (salen)Co(OAc) complexes provides enantiomerically enriched epoxides and diols, which have been transformed into important insect sex pheromones. In this general approach, (-)-(R)- and (+)-(S)-10-methyldodecyl acetates from the smaller tea tortrix moth were obtained, as was (-)-(R)-10-methyltridecan-2-one from the southern corn rootworm. The (S)-epoxide obtained from undec-1-en-6-yne was transformed to (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol) from ant-lions. HKR of appropriate bisepoxides was also investigated, and transformations of the resulting bisepoxides and epoxydiols provided (-)-(1R,7R)-1,7-dimethylnonylpropanoate from corn rootworms, (-)-(6R,12R)-6,12-dimethylpentadecan-2-one from the female banded cucumber beetle, and (-)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane from female pea-midges. (C) 2002 Elsevier Science Ltd. All rights reserved.

High resolution 3-D imaging via multi-pass SAR

Spaceborne/airborne synthetic aperture radar (SAR) systems provide high resolution two-dimensional terrain imagery. The paper proposes a technique for combining multiple SAR images, acquired on flight paths slightly separated in the elevation direction, to generate high resolution three-dimensional imagery. The technique could be viewed as an extension to interferometric SAR (InSAR) in that it generates topographic imagery with an additional dimension of resolution. The 3-D multi-pass SAR imaging system is typically characterised by a relatively short ambiguity length in the elevation direction. To minimise the associated ambiguities we exploit the relative phase information within the set of images to track the terrain landscape. The SAR images are then coherently combined, via a nonuniform DFT, over a narrow (in elevation) volume centred on the 'dominant' terrain ground plane. The paper includes a detailed description of the technique, background theory, including achievable resolution, and the results of an experimental study.

A new technique for the quantification of peripheral edema with application in both unilateral and bilateral cases

Current noninvasive techniques for the routine and frequent quantification of peripheral lymphedema in patients are total limb volume measurement (by water immersion or by circumferential measurements) and bioelectrical impedance analysis (BIA). However both of these techniques require standardizing the measurement using a contralateral measurement from the unaffected limb, Hence these techniques are essentially restricted to unilateral lymphedema. This paper describes the results from a preliminary study to investigate an alternative approach to the analysis of the data from multiple frequency BIA to produce an index of lymphedema without the need for normalization to another body segment. Twenty patients receiving surgical treatment for breast cancer were monitored prior to surgery and again after diagnosis with unilateral lymphedema. The data recorded were total limb volume, by circumferential measurements; and BIA measurements of both limbs. From these measurements total limb volumes and extracellular fluid volumes were calculated and expressed as ratios of the affected limb to that of the unaffected limb. An index of the ratio of the extracellular fluid volume to the intracellular fluid volume was determined. This ECW/ICW index was calculated for both the affected and unaffected limbs at both measurement times. Results confirmed that the established techniques of total limb volume and extracellular fluid volume normalized to the unaffected contralateral limb were accurate in the detection of lymphedema (p < 10(-6)). Comparison of the ECW/ICW index from the affected limb after diagnosis with that from the pre-surgery measurement revealed a significant (p< 10(-6)) and considerable (75%) increase. The results of this pilot study suggest that by using multiple frequency bioelectrical impedance analysis, an index of the ECW/ICW ratio can be obtained and this index appears to have an equal, or better, sensitivity, than the other techniques in detecting lymphedema. More importantly, this index does not require normalization to another body segment and can be used to detect all types of peripheral edema including both unilateral and bilateral lymphedema.

Propagation of nonstationary curved and stretched premixed flames with multistep reaction mechanisms

The propagation speed of a thin premixed flame disturbed by an unsteady fluid flow of a larger scale is considered. The flame may also have a general shape but the reaction zone is assumed to be thin compared to the flame thickness. Unlike in preceding publications, the presented asymptotic analysis is performed for a general multistep reaction mechanism and, at the same time, the flame front is curved by the fluid flow. The resulting equations define the propagation speed of disturbed flames in terms of the properties of undisturbed planar flames and the flame stretch. Special attention is paid to the near-equidiffusion limit. In this case, the flame propagation speed is shown to depend on the effective Zeldovich number Z(f) , and the flame stretch. Unlike the conventional Zeldovich number, the effective Zeldovich number is not necessarily linked directly to the activation energies of the reactions. Several examples of determining the effective Zeldovich number for reduced combustion mechanisms are given while, for realistic reactions, the effective Zeldovich number is determined from experiments. Another feature of the present approach is represented by the relatively simple asymptotic technique based on the adaptive generalized curvilinear system of coordinates attached to the flame (i.e., intrinsic disturbed flame equations [IDFE]).

Distribution kinetics of solutes in the isolated in-situ perfused rat head using the multiple indicator dilution technique and a physiological two-barrier model

The purpose of this study was to determine the pharmacokinetics of [C-14]diclofenac, [C-14]salicylate and [H-3]clonidine using a single pass rat head perfusion preparation. The head was perfused with 3-[N-morpholino] propane-sulfonic acid-buffered Ringer's solution. Tc-99m-red blood cells and a drug were injected in a bolus into the internal carotid artery and collected from the posterior facial vein over 28 min. A two-barrier stochastic organ model was used to estimate the statistical moments of the solutes. Plasma, interstitial and cellular distribution volumes for the solutes ranged from 1.0 mL (diclofenac) to 1.6 mL (salicylate), 2.0 mL (diclofenac) to 4.2 mL (water) and 3.9 mL (salicylate) to 20.9 mL (diclofenac), respectively. A comparison of these volumes to water indicated some exclusion of the drugs from the interstitial space and salicylate from the cellular space. Permeability-surface area (PS) products calculated from plasma to interstitial fluid permeation clearances (CLPI) (range 0.02-0.40 mL s(-1)) and fractions of solute unbound in the perfusate were in the order: diclofenac>salicylate >clonidine>sucrose (from 41.8 to 0.10 mL s(-1)). The slow efflux of diclofenac, compared with clonidine and salicylate, may be related to its low average unbound fraction in the cells. This work accounts for the tail of disposition curves in describing pharmacokinetics in the head.

Hand-assisted laparoscopic adrenalectomy: An alternative minimal invasive surgical technique for the adrenal gland

Background: Presently the surgical approach to the adrenal gland is in a state of flux. While the traditional approach to the adrenal gland has been the open transabdominal technique, more recently laparoscopic approaches, particularly via the transabdominal route, have increasingly been utilized. However, laparoscopic intervention for the adrenal gland can be problematic in certain circumstances, particularly for large adrenal masses and in instances of adrenal malignancies. Methods: In this report we describe the use of hand-assisted laparoscopic adrenalectomy as an alternative minimal invasive surgical approach to the adrenal gland. Hand-assisted laparoscopic adrenalectomy using the HandPort system (Smith & Nephew, Sydney, Australia) was undertaken in three patients requiring adrenalectomy for mass lesions including one patient with Conn's syndrome. Results: In all three cases, surgery proceeded promptly and uneventfully. In the present paper, the details of the technique of hand-assisted adrenalectomy are described. This is the first report in the world literature of this new technique for the adrenal gland. Conclusions: Hand-assisted laparoscopic adrenalectomy is an easily performed technique, which can be completed within a short operative time span and which has the advantage of providing intraoperative tactile localization for the adrenal gland. It may be particularly applicable for large adrenal tumours, yet only involves the performance of a small abdominal incision. Postoperative recovery is comparable with that reported for the laparoscopic-only technique. Hand-assisted adrenalectomy is a new technique which has great potential and which warrants further evaluation.

Structural refinement of systems specified in object-z and CSP

This paper is concerned with methods for refinement of specifications written using a combination of Object-Z and CSP. Such a combination has proved to be a suitable vehicle for specifying complex systems which involve state and behaviour, and several proposals exist for integrating these two languages. The basis of the integration in this paper is a semantics of Object-Z classes identical to CSP processes. This allows classes specified in Object-Z to be combined using CSP operators. It has been shown that this semantic model allows state-based refinement relations to be used on the Object-Z components in an integrated Object-Z/CSP specification. However, the current refinement methodology does not allow the structure of a specification to be changed in a refinement, whereas a full methodology would, for example, allow concurrency to be introduced during the development life-cycle. In this paper, we tackle these concerns and discuss refinements of specifications written using Object-Z and CSP where we change the structure of the specification when performing the refinement. In particular, we develop a set of structural simulation rules which allow single components to be refined to more complex specifications involving CSP operators. The soundness of these rules is verified against the common semantic model and they are illustrated via a number of examples.

A technique to assess small-scale heterogeneity of chemical properties in soil aggregates

A new method is presented which allows the separation of the soil aggregate exterior from the aggregate core. The method employs a combination of aggregate freezing with rapid separation of aggregate exteriors using ultrasonic energy. The factors influencing the thickness of the removed aggregate surface layer include water content of the aggregate prior to freezing, temperature difference between that of the frozen aggregate and that of the liquid it is submerged in during sonification, sonification time and energy, and the type of the immersion liquid. The success of the method and the thickness of the removed aggregate surface were examined using barium ( Ba2+) as a tracer. Barium ( as BaCl2) is rapidly absorbed by soil and is present at only very low levels in natural soils. Surface layers of 0.2 - 0.4 cm thickness were successfully removed from aggregates of 1 - 4 cm diameter. Two examples are given from soils in northern NSW to demonstrate the occurrence of small- scale heterogeneity in soil chemical properties. Compared with the surface fraction, a 4 - 7% higher calcium concentration was found in the core fraction of a clay loam soil ( Dermosol). Conversely, on a cracking clay soil ( Vertosol), atrazine concentration was around 15 times greater in the aggregate surface fractions compared with core fractions. Compared with the traditional estimation of soil chemical properties on homogenised bulk soil samples, it is suggested that separate analysis of aggregate surface and core fractions could provide useful additional information on the relationships between soil properties and environmental responses.